Decomposition of multi-peroxidic compounds

Part II. Hexamethylene triperoxide diamine (HMTD)

J.C. Oxley
a,*
, J.L. Smith
a
, H. Chen
a
, Eugene Ciof
b
a
Chemistry Department, University of Rhode Island, Kingston, RI 02881, USA
b
University of South Alabama, Kingston, RI 02881, USA
Received 24 June 2001; received in revised form 4 September 2001; accepted 8 September 2001
Abstract
The thermal decomposition of neat hexamethylene triperoxide diamine (HMTD) was examined over the temperature range
100 and 180 8C. It was found to be rst-order up to 150 8C and produce ~2 mole of gas/mole HMTD; primarily CO
2
but also
trimethylamine and ammonia. Above 150 8C, the decomposition became nearly instantaneous and gas production more than
doubled. Instead of carbon dioxide, CO was the main product (about 3 mole/mole HMTD) and under air no trimethylamine was
observed from the thermolysis. The observed changes in products may indicate a change in mechanism, but they can also be
explained by a secondary reaction, the oxidation of trimethylamine to HCN and methanol. The latter interpretation is based on
the fact that when available oxygen was limited, i.e. when the decomposition was performed under vacuum, some
trimethylamine was observed in the high temperature thermolysis. Two possible mechanisms are suggested, one free radical
and the other ionic. # 2002 Elsevier Science B.V. All rights reserved.
Keywords: Hexamethylene triperoxide diamine; DSC
1. Introduction
Hexamethylene triperoxide diamine (HMTD) was
rst synthesized around 1900 and initial studies
focused on its synthesis and on determining its struc-
ture [1]. As late as 1967 Urbanski proposed two
possible structures for HMTD, but by 1984 NMR
showed the structure to be that rst proposed in
1900 (Fig. 1) [2]. This was conrmed a year later
by X-ray crystallography and more recently by density
functional theory calculations [3,4]. The structure of
HMTD is unusual because the N(CH
2
)
3
group is
exactly planar and symmetrical about the bridgehead
nitrogens, the extreme sensitivity of HMTD may be
related to this feature. In the 1940s and into the 1960s
the military examined HMTDfor possible applications;
[2,5] however, its extreme sensitivity made commercial
or military applications unsafe. Recently, it has found
use by terrorists because of ease of synthesis and
availability of starting materials [6]. The present study
is part of a series examining the stability of multi-
peroxidic compounds under the inuence of electron
impact or thermal decomposition [7,8].
2. Experimental section
Synthesis of HMTD, both labeled [
15
N(
13
CH
2
O
O
13
CH
2
)
3
15
N] and unlabeled, has been previously
reported [7]. The basic synthetic procedure used hex-
amethylene tetramine and hydrogen peroxide with
Thermochimica Acta 388 (2002) 215225
*
Corresponding author.
E-mail address: joxley@chm.uri.edu (J.C. Oxley).
0040-6031/02/$ see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S0 0 4 0 - 6 0 3 1 ( 0 2 ) 0 0 0 2 8 - X
citric acid catalyst [4]. As prepared, HMTD is a white
crystalline solid, insoluble in water and common
organic solvents such as methanol, acetonitrile and
acetone. Although, HMTD has slight solubility in
chloroform (0.64 g/100 g), [1] its solubility was too
low to use conventional liquid chromatography and it
was too labile to permit use of gas chromatography to
determine kinetics. Complete decomposition of
HMTD at low temperatures, such as in the isothermal
studies described below, left a small amount of color-
less liquid (which is probably trimethylamine). How-
ever, in differential scanning calorimetry (DSC)
studies, which took HMTD to very high temperatures,
only a very small amount of black or brown residue
remained.
The thermal stability of HMTD was evaluated using
DSC. Samples (0.10.4 mg) were sealed in capillary
tubes (1:5 mmo:d: 10 mm) which were held in an
aluminum cradle [9] under nitrogen ow inside the
head of a TA Instruments 2910 DSC, which was
calibrated against indium. The thermograms of HMTD
were obtained over the temperature range 40500 8C.
The American Society for Testing and Materials
(ASTM) differential heating rate method was used to
calculate Arrhenius parameters [10]. A plot of log
10
b
(b is heating rate in 8C min
1
) versus 1/T (T is the
exothermic peak temperature in kelvin) was made. An
approximation of the activation energy (E
a
) could be
calculated from the slope, 2.19R[d(log
10
b)/d(1/T)]
(where R is the gas constant). A renement of the
activation energy and an estimation of the Arrhenius
pre-exponential factor (A) were calculated according to
the ASTM protocol [10].
Isothermal thermolyses were performed in an oven
on samples (0.10.6 mg) in tubes 4 mm o:d: 50 mm
to measure kinetics or in narrower tubes (1.21.5 mm
o:d: 50 mm) to determine decomposition gases.
Total decomposition was estimated by heating HMTD
until no further gas formed. This was used to deter-
mine the fraction reacted for calculation of kinetics.
After the sample was heated for a specied time
interval, the tube was broken into a gas manometer
(to assess amount of gas produced) or into a GC (to
assess gas composition). The decomposition gases
were identied by gas chromatography/mass spectro-
metry (GC/MS) [11]. A HP Model 5890 Series II GC,
equipped with model 5971 electron impact mass
selective detector, helium carrier gas and PoraPLOT
Q (0:25 mm25 mm) column from Chrompack was
used [11]. Decomposition gases were identied by
comparing their GC retention times and mass spectra
to authentic samples. When authentic samples were
not available, sample spectra were compared with the
NIST MS library for tentative assignment. To quantify
the permanent gases, a HP 5890 series II GC with a
thermal conductivity detector (GC/TCD) and Hayesep
DB 100/120 (30 in: 1=8 in.) column (Alltech) was
used.
3. Results
A typical DSC scan of HMTD, shown in Fig. 2,
consisted of a single sharp exotherm at about 165 8C
(y = 20 8C min
1
). Arrhenius parameters were calcu-
lated from the DSC data using the ASTM method. At
150 8C and below rst-order rate constants were cal-
culated fromisothermal heating (Table 1). However, at
160 8C HMTD decomposition went from 90%
remaining to 0% remaining in the rst 45 s. Arrhenius
parameters derived by the DSC variable heating rate
method (E
a
= 164:7 kJ/mol, A = 1:49 10
18
s
1
)
and those derived from monitoring evolved gas
(E
a
= 107 kJ/mol, A = 4:21 10
10
s
1
) are given in
Table 1. These parameters differ signicantly and the
isothermal results should be those relied on. However,
it is interesting to note the rate constants calculated
from these parameters do not differ greatly, an exam-
ple of the kinetic compensation effect [12].
To analyze for the decomposition products of
HMTD, samples were heated in air and in vacuum
over the temperature range 100180 8C. GC/MS was
used to identify the products and GC/TCD to quantify
them. GC/TCD analysis indicated that the prominent
Fig. 1. Structure of HMTD and TATP.
216 J.C. Oxley et al. / Thermochimica Acta 388 (2002) 215225
gas at 150 8Cand belowwas CO
2
, at 160 8Cand above
there was a major change in the decomposition pro-
ducts just as there was in the kinetics. CO
2
became the
minor carbonaceous gas and CO, the major one
(Table 2). At or below 150 8C the fate of nitrogen
was to form trimethylamine and presumably ammonia
(Fig. 3, Eq. (1)). Trimethylamine was readily identi-
ed by GC/MS but was not quantied. By the GC/MS
technique it was difcult to differentiate between
ammonia and water. Both had retention times of about
19 min and masses 17 and 18 were both prominent
fragments. We believe the peak at 19 min is a mixture
of water and ammonia and a water/ammonia mixture
produced similar fragmentation patterns.
At 160 and 180 8C, trimethylamine was not
observed in the thermolyses performed in air; how-
ever, it was observed in those performed in vacuum
(Figs. 4 and 5). Eq. (2) is meant to convey the basic
products from the high-temperature thermolysis of
HMTD; however, it should be noted that the forma-
tion of molecular oxygen was not observed. Several
oxygenated hydrocarbons were observed instead; oxy-
gen appears in this formula only for the sake of
simplicity and stoichiometry.
C
6
H
12
O
6
N
2
3CO
2
N(CH
3
)
3
NH
3
(at or below150

C; air or vacuum)
(1)
HMTD
C
6
H
12
O
6
N
2
3CO N(CH
3
)
3
0:5N
2
1:5H
2
O
0:75O
2
(160180

C; vacuum)
(2)
We suspected the reason trimethylamine was not
observed in the high temperature thermolysis was
due to its reactivity. A literature search revealed that
trimethylamine reacts with molecular oxygen at tem-
peratures as low as 165 8C, though the reaction does
not go to completion [13]. Cullis and Waddington [13]
studied the oxidation of trimethylamine and triethy-
lamine and found their oxidations self-inhibiting.
Fig. 2. DSC Thermogram of HMTD (20 8C min
1
).
J.C. Oxley et al. / Thermochimica Acta 388 (2002) 215225 217
Table 1
DSC and isothermal kinetics
Scan rate, b
(8C/min)
Exothermic maximum
temperature
Heat released Number
of runs
T (8C) K R
2
Fraction
remained (%)
Atmosphere T (8C) k (ASTM) k (gas)
8C K J/g cal/g
DSC exotherms of HMTD at various scan rates
a
Isothermal first-order rate constants for neat HMTD
b
Rate constants calculated from
Arrhenius parameters
20 164 437 3285 793 3 100 4.95E05 0.96 0.070 Air 100 6.2E06 3.0E05
10 157 431 3418 825 3 120 2.96E04 0.95 0.082 Air 150 3.6E03 1.8E03
5 152 426 4255 1027 2 140 1.14E03 0.95 0.299 Air
2.5 146 419 4143 1000 3 150 3.26E03 0.95 0.440 Air
1 138 411 4207 1016 2 160 Completely gone in less than 45 s Air
160 Vacuum
a
E
a
(kJ/mol) 165 = 39:4 kcal/mol; A (s
1
) 1:5E18, R
2
= 0:998 DSC.
b
Neat 1001508C, E
a
(kJ/mol) 107 = 25:5 kcal/mol, A (s
1
) 4:21E10, R
2
= 0:995 isothermal.
2
1
8
J
.
C
.
O
x
l
e
y
e
t
a
l
.
/
T
h
e
r
m
o
c
h
i
m
i
c
a
A
c
t
a
3
8
8
(
2
0
0
2
)
2
1
5

2
2
5
Table 2
HMTD decomposition products under various experimental conditions
Temperature (8C) atmosphere
180 8C 160 8C 150 8C 140 8C 120 8C 110 8C 100 8C
Vacuum
a
Vacuum Air
a
Air Air Vacuum Vacuum Air Air Vacuum Air Air Vacuum Air Air Vacuum Air Air Air Vacuum Vacuum Air Air Vacuum
Hours heated 0.67 0.67 0.67 2.25 0.7 1 1.67 1 0.5 4.25 4.75 3.5 4 9.5 21.33 11.5 17.3 2.75 30 1 1.25 25.25 40.3 1.75
Fraction
decomposed
1 1 1 1 Label 1 1 1 1 1 1 1 1 1 1 1 1 1 0.17 0.05 1 1 Label
Sample (mg) 0.13 0.12 0.18 0.10 0.14 0.11 0.19 0.42 0.39 0.15 0.13 0.22 0.27 0.29 0.31 0.36 0.30 0.40 0.29 0.75 0.45 0.38 0.50 0.57
mol gas/mol HMTD
N
2
0 0.2 0.3 0 0.10 0.4 0 0.10 0 0 0 0 0.12 0.04 0.00
CO
2
0.2 0.4 0.4 0.3 0.3 0.3 1.4 2.0 2.1 1.9 2.0 1.9 1.9 1.9 1.9
CO 2.6 3.9 3.8 3.1 3.1 2.9 1.1 0.2 0.1 0.2 0.2 0.1 0.1 0.1 0.1
Total gas by GC 2.9 4.5 4.5 3.3 3.5 3.3 2.5 2.2 2.2 2.0 2.1 2.0 2.1 2.0 2.0
Total gas by
manometer
3.9 6.1 6.1 2.8 5.1 5.0 1.9 3.1 1.8 2.6 1.6 2.4 2.4 2.3
RT GC estimates of relative amounts (%)
CO
2
14 100 80 100 100 100 74 100 100 100 40 47 33 51 61 59 29.1 61 66 100 100 100 61 58 100
N(CH
3
)
3
27 73 100 79 100 100 100 100 100 100 100 100 100 t 13 18 100 100 35
CO 4.8 t s 31 22 36 2.4 7.7 70 55 t t t t t t t t t t t t t 0.8
HCN 21 12 7 13 14 s
NH
3
/H
2
O 19 s s s 10 s s s 10 3.0 s s s s 1.9 s s 2.9 s s 1.7 3.9 3.2 2.1 3.1
HCOOCH
3
24 t t t t t t 2.5 t 8 t t s t t t t t t t t t
N
2
3.5 t 11 13 14 15 11 2 1 2.3 1.9 t 2.5 2.5 9.4 2.2 1.8
O
2
3.9 t t t 1.0 0.5 0.6 0.4 1.1 0.9 0.7 0.7
CH
3
OH 22 t t t t t t 13 9 t t t t t t t t t t t
CH
3
CN 26 t t t t t t 6 s
(CN)
2
t t t
CH
3
COOH 29 t 14 t
HCOOH 27 t t t 2.4
Below detection limits: (); RT: retention time (min); t: trace; s: some.
a
Atmospheric conditions.
Fig. 3. Chromatogram HMTD heated in air 140 8C.
Fig. 4. Chromatogram HMTD heated in air 180 8C.
220 J.C. Oxley et al. / Thermochimica Acta 388 (2002) 215225
Triethylamine decomposed by two routes, forming
monoethylamine by the unimolecular decomposition
of an intermediate peroxy-radical, or producing
diethylamine by capping of the peroxy radical to form
a hydrogen peroxide which then reacted with a second
molecule of triethylamine to form the diamine and
acetaldehyde. In contrast, the oxidation of trimethy-
lamine did not produced mono-methylamine, it
formed formaldehyde, dimethylamine and nitrogen.
The authors speculated that steric hinderance made
oxidation of trimethylamine difcult.
In the thermolysis of HMTD we observed neither
formaldehyde nor dimethylamine. Our experimental
conditions are such that we would not expect to
observe formaldehyde, but dimethylamine should be
observable if formed. This difference in decomposi-
tion products may be due to differences in experi-
mental conditions (although the temperature and
reactant concentrations are similar); or perhaps, in
the decomposition of HMTD, oxygen is reacting
with a trimethylamine precursor. From examination
of the decomposition products of HMTD at 160 and
180 8C in vacuum and in air, we surmised that the
ultimate fate of trimethylamine or its precursor is to be
converted to hydrogen cyanide and methanol.
N(CH
3
)
3
O
2
HCN 2CH
3
OH (3)
4. Discussion
HMTD is sufciently shock sensitive that it has
been used as a primary explosive [6]. In contrast
triacetone triperoxide TATP, a monocyclic triperoxide
is much more stable. While explosive performance is
frequently assessed by detonation velocity (4.5 km/s
for HMTD and 5.2 km/s for TATP), [2] sensitivity to
ignition is judged by a number of tests, a common one
is drop mass impact. In the most common form of the
drop mass impact test, a 40 mg sample is placed on an
anvil and a weight (2 or 5 kg) is dropped on it. A ``go''
is determined by a loud report; multiple tests are
performed [14]. Drop mass impact values for HMTD
and TATP are reported as 3 and 10 cm, respectively,
[2,15]. These impact stabilities are reected by their
thermal stabilities. For example their rst order
decomposition rate constants at 150 8C differ by three
orders of magnitude [3 10
3
s
1
(HMTD) and
Fig. 5. Chromatogram HMTD heated in vacuum 180 8C.
J.C. Oxley et al. / Thermochimica Acta 388 (2002) 215225 221
7 10
6
s
1
(TATP)]. The correlation between sen-
sitivity to drop weight and thermal stability has long
fascinated those studying energetic materials [16,17]. A
classic case is that of 1,3,5-trinitro-2,4,6-triaminoben-
zene which is well-known for both high thermal stability
and high resistance to drop mass impact [18]. Logically,
both sensitivities should have their basis in thermal
stability. The problem with the correlation, however,
is that drop mass and thermal stability are generally
examining different temperature regimes [19]. It is not
surprising that HMTD should be much more shock
sensitive than TATP. HMTD has unusual bond strain
with the carbons arranged in exact three-fold coordina-
tion about the two bridgehead nitrogen atoms [3,4].
Ring strain provides extra energy to the detonation of
energetic materials, but it is probably also a source of
enhanced sensitivity, e.g. nitrocubanes [20,21].
An unusual feature of HMTD decomposition was
the apparent sudden change in rate and decomposition
products that occurred between 150 and 160 8C. In the
low temperature regime, thermolyses in air and
vacuum gave essentially the same products CO
2
and
trimethylamine. At high temperature the principal
carbon-containing product was CO not CO
2
; and
trimethylamine was not observed for thermolyses
performed in air. At and below 150 8C, the decom-
position of HMTD is reasonably rst-order. At 160 8C
instantaneous decomposition appeared to follow a
brief induction period. In examining the decomposi-
tion of TATP we considered several possible decom-
position mechanisms: concerted loss of O
2
or stepwise
decomposition, initiated by OO homolysis or
initiated by CO homolysis. The experimental results
showed the decomposition was stepwise with OO
homolysis the initiating step. The principle products
observed were acetone and carbon dioxide, but mole-
cular oxygen could have been formed and subse-
quently reacted. It was concluded that the same
pathway remained dominant over a wide temperature
range (150235 8C) although at high temperatures
formation of methyl radical by CC homolysis
became noticeable.
Following decomposition reactions analogous to
those proposed for TATP we considered four possible
homolytic decomposition routes for HMTD: two con-
certed; two stepwise; two involving OO homoly-
sis; and two involving CO homolysis (Fig. 6).
Postulating OO homolysis (routes (b) and (c)) made
direct formation of trimethylamine difcult to explain.
For a bridgehead nitrogen to retain its original methy-
lene groups yet form trimethylamine, OCH
2
NR
2
must be transformed to CH
3
NR
2
. If the bridgehead
nitrogen does not retain its original methylene groups
but forms trimethylamine by gaseous interactions of
smaller molecules, it would seem likely that other
methylamines (mono and di) would also be formed.
However, under none of our experimental conditions
were monomethylamine or dimethylamine observed.
Both routes (a) and (d) postulate CO bond clea-
vage. The unique structure of HMTD may cause C
O cleavage to be favored over the OO homolysis
typical for peroxides. Cleavage of CO would
relieve ring strain and allow straight-forward produc-
tion of trimethylamine. However, the concerted route
(a) undoubtedly would be of high energy and very
unlikely. Of the four homolytic routes considered,
route (d), loss of molecular oxygen, would appear
most reasonable and produce the observed products.
However, the ionic decomposition pathway shown in
Fig. 7 would also produce the observed products.
Peroxides frequently decompose by homolytic O
O cleavage; however, we postulate that is not the case
for HMTD. HMTD may be unique in that it may use
an ionic decomposition pathway. Certainly at 160 8C
there is an abrupt change in rate and reaction products.
The change in reaction products can be explained
without postulating a change in mechanism, however,
the rapid acceleration of decomposition observed may
be best explained by a change from an ionic (Fig. 7) to
a free radical (Fig. 6d) decomposition route. Labeling
studies do not differentiate between these two routes,
but use of radical trapping agents might. To date we
have not probed the high temperature regime because
decomposition is close to instantaneous.
The observed decomposition products at low or
high temperatures can be explained without a change
in mechanism. As implied by Eq. (2) we believe
trimethylamine is formed over the entire temperature
range studied (100180 8C). However, at 160 8C and
above, when levels of molecular oxygen were suf-
cient (possibly after a brief induction period) that the
oxygen attacked the amine so that trimethylamine was
not observed. Considered as an explosive, HMTD is
oxygen decient, i.e. it does not contain sufcient
oxygen to convert all hydrogen atoms to water and all
carbon to CO or CO
2
. TATP has a similar deciency,
222 J.C. Oxley et al. / Thermochimica Acta 388 (2002) 215225
Fig. 6. Possible homolytic decomposition routes of HMTD.
Fig. 7. Proposed ionic decomposition route of HMTD.
J.C. Oxley et al. / Thermochimica Acta 388 (2002) 215225 223
but under thermolysis conditions TATP produces acet-
one, thus, using only one oxygen atom to tie up three
carbon and six hydrogen atoms. The low-temperature
decomposition of HMTD ties up three carbons and
nine hydrogen in trimethylamine; thus, there were
sufcient oxygen atoms to convert the remaining three
carbons to CO
2
or CO. Under conditions where tri-
methylamine is oxidized, there is insufcient oxygen.
Reaction (2) leaves 0.75 mole of O
2
, but for reaction
(3) to go to completion another 0.25 mole of molecular
oxygen is required. At the normal scale of our experi-
ments, the air-lled reaction tubes provided 0.50.7
mole of molecular oxygen per mole HMTD; there was
just sufcient oxygen to destroy all trimethylamine.
However, under vacuum some trimethylamine sur-
vived. Therefore, the change in thermolysis products
observed at and above 160 8C can be explained by a
secondary reaction (of trimethylamine). However,
while an abrupt change in mechanism need not be
postulated to explain the change in products, it may
explain the dramatic increase in decomposition rate
observed at and above 160 8C.
5. Conclusions
The thermal decomposition of HMTD is initiated by
a rst-order elimination of O
2
. The need to eliminate
ring strain makes this a relatively low temperature and
fast event compared to the decomposition of TATP. Two
mechanisms for oxygen elimination have been pro-
posed, ionic and free radical. While experimental data
cannot distinguish between them, the rapid increase in
decomposition rate observed between 150 and 160 8C
suggests the dominant mechanism may switch from
ionic to free radical in that temperature range. Subse-
quent decomposition of the remaining species results in
the products CO
2
, trimethylamine and ammonia at
temperatures of 150 8C or less. Above 150 8C a sec-
ondary reaction becomes important, the oxidation of
the trimethylamine to HCN and methanol. Due to the
increased number of carbons to be oxidized, carbon
monoxide rather than carbon dioxide was the major
carbonaceous product in the high temperature thermo-
lysis. When oxygen was limited by performing the
thermolysis in vacuum, there was insufcient oxygen
to oxidize all the trimethylamine and some was
observed in the decomposition products.
Acknowledgements
We thank the FAATechnical Center for funding this
research.
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